Dioxolanyl carbonyl ureas and thioureas

ABSTRACT

New compounds of the formula   WHEREIN R1 and R2 each is alkyl; R3 is substituted carbamoyl or thiocarbamoyl; and R4 is optionally substituted phenyl, are useful as herbicides.

United States Patent [1 1 Isaac et al.

[ DIOXOLANYL CARBONYL UREAS AND THIOUREAS {75] Inventors: Eirlys R. Isaac, Sittingbourne; Peter Kirby, Maidstone, both of England {73] Assignee: Shell Oil Company, Houston, Tex.

[22] Filed: June 25, 1974 [2]] App]. No: 482,936

[30} Foreign Application Priority Data July 3 1973 United Kingdom 31604/73 [52] US. Cl 260/3403; 71/88 [S 1} Int. Cl r. C07c 127/22; C07c l57/22 [58] Field of Search 260/3409 l 56} References Cited OTHER PUBLICATIONS Smith. The Chemistry of Open-Chain Organic Nitrogen Compounds. Vol. 1, page [49 June 24, 1975 Kirby et 211., Chemical Abstracts, Vol. 78 (1973) 72ll2w.

Primary ExaminerLorraine A. Weinberger Assistant Examiner-Richard L. Raymond wherein R and R each is alkyl; R is substituted carbamoyl or thiocarbamoyl; and R is optionally substituted phenyl, are useful as herbicides.

4 Claims, No Drawings DIOXOLANYL CARBONYL UREAS AND THIOUREAS DESCRIPTION OF THE INVENTION This invention relates to amide derivatives which are of interest as herbicides.

Accordingly the present invention provides amide derivatives of general formula:

on o n I 2 \C/ 2 I a c cowrs crr ocn n wherein R, and R each represents an alkyl group; R represents a carbamoyl or thiocarbamoyl group N- substituted by alkyl, haloalkyl, cycloalkyl, phenyl, alkylphenyl, halophenyl, nitrophenyl, alkoxyphenyl or by alkenyl of 2 to 6 carbon atoms, and R represents a phenyl group optionally substituted by halogen or by alkyl.

More particularly, the invention is directed to amide derivatives of general formula I wherein R, and R each represents an alkyl group of 1-6 carbon atoms; R represents a carbamoyl or thiocarbamoyl group N- substituted by alkyl, haloalkyl or cycloalkyl of up to 6 carbon atoms, by phenyl, alkylphenyl, nitrophenyl, alkoxyphenyl or fluoroor chlorophenyl of up to 8 carbon atoms, and R represents a phenyl group optionally substituted by fluorine or chlorine or by an alkyl group of l-6 carbon atoms.

Examples of such compounds include those species described in Examples 1-20 hereinafter; also, the following species are contemplated, as well:

N-( (4-beniyloxymethyl-2-methyl-4-ethyl-l ,3-

dioxolan-2-yl)carbonyl)-N'-( 2-nitrophenyl)urea N-( (4-benzyl0xyrnethyl-2-methyl-4-ethyl-l ,3-

dioxolan-Z-yl)carbonyl)-N'-(3- methoxyphenylJurea N-((4-benzyloxymethyl-2-methyl-4-ethyl-l ,3-

dioxolan-2-yl)carbonyl)-N'-chloromethylurea N-( (4-benzyloxymethyl-2-methyl-4-ethyl-l ,3-

dioxolan-2-yl)carbonyl)-N'-methylthiourea N-( (4-benzyloxymethyl-2-methyl-4-ethyl-l ,3-

dioxolan-2-yl)carbonyl)-N'-phenylthiourea Because of their properties, preferred amide derivatives are those of formula I wherein R, and R each represents an alkyl group of 1-6 carbon atoms, for example methyl, ethyl, or propyl; R represents a carbamoyl group N-substituted by alkyl or cycloalkyl of up to 6 carbon atoms, for example by methyl, ethyl or by cyclohexyl, or by phenyl, tolyl or dichlorophenyl; and R represents a phenyl group optionally substituted by one or two chlorine atoms or by an alkyl group of 1-6 carbon atoms, for example by methyl.

Most active, and therefore most preferred amide derivatives appear to be those of formula I wherein R, represents methyl, ethyl or propyl; R represents methyl; R represents a carbamoyl group N-substituted by methyl, ethyl, propyl or butyl; and R, represents phenyl optionally substituted by one or two chlorine.

Preferred species of this subclass include:

N-( (4-benzyloxymethyl-2-methyl-4-ethyl-l ,3-

dioxolan-Z-yl )carbonyl )-N 'methylurea N-( 4-benzyloxymethyl-2-methyl-4-n-propyll ,3-

dioxolan-Z-yl )carbonylJ-N 'methylurea N-( (4-benzyloxymethyl-2,4-dimethyll ,3-dioxolan- 2-yl)carbonyl)-N'butylurea The compounds of formula I may be prepared by a process which comprises reacting a compound of formula wherein R represents a hydrogen atom with an isocyanate of the formula R NCO or an isothiocyanate of formula R NCS wherein R represents an alkyl, haloalkyl, cycloalkyl, phenyl, alkylphenyl, halophenyl, nitrophenyl, alkoxyphenyl or alkenyl group, The compounds of formula I wherein R is hydrogen are known compounds, disclosed in Netherlands Pat. No. 72,07026.

As mentioned above the amide derivatives of the invention are of interest as herbicides, and the invention includes, therefore, herbicidal compositions comprising a carrier and/or a surface active agent, together with, as active ingredient, an amide derivative of the invention. Likewise the invention also includes a method ofcombating weeds at a locus which comprises applying to the locus an amide derivative or composition of the invention.

The term carrier" as used herein means a solid or fluid material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport or handling. stabiliser(s) The surface-active agent may be an emulsifying agent or a dispersing agent or a wetting agent; it may be nonionic or ionic.

Any of the carrier materials or surface-active agents usually applied in formulating pesticides may be used in the compositions of the invention, and suitable examples of these are to be found, for example, in UK specification No. 1,232,930.

The compositions of the invention may be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols. wettable powders are usually compounded to contain 25, 50 or w of toxicant and usually contain, in addition to solid carrier, 3l0% w of a dispersing agent and, where necessary, 0- l 0% w of stabilisers(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing 10% w of toxicant. Granules are usually prepared to have a size between 10 and BS mesh (l.676-0.l52 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain %25% w active ingredient and 0-l0% w of additives such as stabilisers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w/v active ingredient, 2-20% w/v emulsifiers and 020% w/v of appropriate additives such as stabilisers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, nonsedimenting, flowable product and usually contain 10-75% w active ingredient, 05-15% w of dispersing agents, 01-10% w of suspending agents such as protective colloids and thixotropic agents, 0-l0% w of appropriate additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and as carrier, water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or should not be regarded as limiting the invention in any way ln the examples the structure of the compounds was confirmed by elemental analysis and NMR spectral analysis.

inorganic salts may be dissolved in the carrier to assist t f EXAMPLE 1 in preventing sedimentation or as anti reeze agen s or water. N-( 4-benzyloxymethyl-2,4-dimethyl-l ,3-dioxolane-2- Aqueous dispersions and emulsions, for example, b n-N- h n lurea compositions obtained by diluting a wettable powder or 4-Benzyl0xymethyl-2A-dimethyl l ,3-dioxane-2- a concentrate according to the invention with water, carboxamide (4.5g) and phenyl isocyanate (2.0g) in also lie within the scope of the present invention. The toluene (50 ml) were heated together under reflux for said emulsions may be Of the WHlCf-ll'l-Oll Of Of the Ollhours The toluene was then removed from [he mmnyp and y have a thlck maYOnIIHISa-lIKe ture under reduced pressure. The residue was trituconsistency. rated with petroleum ether (b.p. -60C) and recrys- The compositions of mvemlo y also 6011mm tallized from ethanol to give the required product m.p. other ingredients, for example, other compounds pos- 91 94C sessing pesticidal, especially insecticidal, acaricidal, herbicidal or fungicidal properties. EXAMPLES 2 20 The invention is further illustrated by the following F ll wi ro edures imilar to those given in the examples. It should be understood, however, that the 20 previous E l fu ther om ound were prepared, examples are for the Pu pose Of u io nly and for which physical characteristics are given in Table l.

TABLE l m.p.C Example Compound or refractive index 2 N-((4-benzyloxymethyl-4-ethyl2-methyl-l ,3- mp.

dioxolan-Z-yl)carhonylyNphenylurea IOU-H12 3 N-( 4-benzyloxymethyl-2.4-dimethyll ,3-dioxom.p.

lan-2-yl )carbonyl )-N 3,4-dichlorophenyl )urea [29- l 34 4 N-( 4-benzyloxymethyl-2,4-dimethyl-l ,3-dioxom.p.

lan-Z-yl lcarbonylJ-N m-tolyl )urea IO'I-l l0 isomer A 5 N-t(4-benzyloxymethyl-2,4-dimethyl-l,B-dioxon L523? lan-2-yl )carhonyl )-N '(m-tolyl )urea isomer B 6 N-( (4-benzyloxymethyl-2,4-dimethyl-l ,3-dioxo m.p.

lan-2-yl )carhonyl )-N 'cyclohexylurea 120- l 22 7 N-( (4-benzyloxymethyl-2.4-dimethyll ,3-dioxom.p.

lan-Z-yl]carbonyl)-N'-methylurea l l3-l l6 8 N-((4-benzyloxymethyl-4 ethyl-2-methyll .3- mp.

dioxolan-Z-yl )carbonyl )-N -methylurea l24 l 26 9 N-( (4-benzyloxymethyl-2-methyl-4-propyl-l ,3- mp.

dinxolan-Z-yl )carbonyl )-N '-methylurea l 10-l 12 ll) N-( (4-benzyloxymethyl-Z,A-dimethyl-l .3-dioxomp.

lan-2-yl)carhonylN butylurea 76-78 I l N-((4benzyloxymethyl-2,4-dimethyl-l ,3-dioxo' m.p.

lan-2-yl)carbonyl)N-ethylurea -9! l2 N-( 4-( 2,6-dichlorobenzyloxymethyl )-4-ethyl-2- m.p.

methyl-l ,3-dioxolan-2-yl )carbonyl)-N'- l09-l2l methylurea l 3 N-( 4-benzyloxymethyl )4-ethyl2-methyll ,3- mp.

dioxolan-2ylcarbonyl)-N"ethylurea l l [-1 l4 l4 N-(4-benzyloxyrnethyl-4-ethyl-2-methyl-l,3- m.

dio xolan-Z-ylcarbonyl )-N -butenylurea 96- i 00 [5 N 4-berizyloxymethyl-2-methyl-4-n-propylm.p.

l,3-dioxolan-2ylcarb0nyl)-N'- henylurea 9l-93 l6 N-(4-(4-fluorobenzyloxyrnethy )-4-ethyl-2- m.p.

methyl-l .S-dioxolan-Z-ylcarbonyl) -93 phenylurea I isomer mixture 17 N-( 4-( 4-fluorobenzyloxymethyl )-4-ethyl-2- m.p.

methyl-l .3-dioxolan-2-ylcarbonyl)-N'- l 10-] I 2 phenylurea isomer B [8 N-( 4-( 4-fluorobenzyloxymethyl )-4-ethyl2- m.p.

methyll ,3-dioxolan-2-ylcarbonyl )-N 84-86 butylurea isomer B l) N-(4-fluorobenzyloxymethyl-4-ethyl-2-methylm.p.

l ,3-dioxolan-2-ylcarbonyl )-N 3,4-dichloro- 1 l8- l 20 phenyllurea isomer B 20 N-( 4fluorobe nzyloxy methyl-4-ethyl- Z-methylm.p.

l ,3-dioxolan-2-ylcarbonyl )-N 3.4-dichloro- 97-l07 phenyl )urea I isomer mixture applied at one dosage level equivalent to l kilograms EXAMPLE 2] of active material per hectare in a volume equivalent to approximately 3,000 litres per hectare.

Herbicidal Activity To evaluate their herbicidal activity, compounds of The herbicidal effects of the compounds were asthe invention were tested using as a representative sessed visually seven days after spraying the foliage and drenching the soil and eleven days after spraying the soil, and were recorded on a 0-9 scale. A rating 0 indicates no effect on the treated plants, a rating 2 indicates a reduction in fresh weight of stem and leaf of the plants of approximately a rating 5 indicates a rerange of plants: maize, Zea mays (M2); rice, oryza sativa (R): barnyard grass, Echinchloa crusgalli (BG); pea, Pisum sativum (P); linseed, Linum usitatissium (L); mustard, Sinapt's alba (M); and sugar beet, Beta vulgaris (SB).

The tests fall into two categories, pre-emergence and duction of approximately 55%, a rating 9 indicates a post-emergence. The pre-emergence tests involved reduction of 95% etc. spraying a liquid formulation of the compound onto the The results of the tests are set out in Table 2.

TABLE 2 Pre-emergence Post-emergence Soil Spray Foliar Spray R 86 Soil Drench R 86 Example Dosage MzRBG M2 PLMSB Mz PLMSB kg/ha 4 7. U U U U 3 4 4 8 3 4 4 2 I 3 0 0 4 2 3 6 4 1D 6 5 6 3 h 7 5 U 7 7 7 9 8 O0 9 3 1D 6 7 i 0 0 2 4 4 4 9 9 2 7 3 7 a 8 7 8 8 8 8 8 9 9 7 7 8 5 5 n1 0 6 6 7 9 9 7 8 6 u 6 5 7 0 0 7 7 8 8 U 9 6 7 I 2 3 4 5 6 7 8 g 1 soil in which the seeds of the plant species mentioned We claim: above had recently been sown. The post-emergence 1. An amide derivative of the formula tests involved two types of test, viz. soil drench and foliar spray tests. In the soil drench tests the soil in which seedling plants of the above species were growing, was

The soil used in the tests was a steam-sterilized, modified John Innes Compost mixture in which half the CH OCH R peat, by loose bulk, had been replaced by vermiculite.

wherein R, and R each represents an alkyl group of 1-6 carbon atoms, R represents a carbamoyl, or thio- The formulations used in the tests were prepared by diluting with water solutions of the compounds in acecarbamoyl group N-substituted by alkyl, haloalkyl or tone containing 0.4% by weight of an alkylphenol/ethylene oxide condensate available under the trade name Triton X-l55. in the soil spray and foliar spray tests the cycloalkyl of up to 6 carbon atoms, by phenyl, alkylphenyl, nitrophenyl, alkoxy-phenyl, or fluoroor chloacetone solutions were diluted with an equal volume of p y of "P to 8 Carbon atoms. y alkenyl of "P to 6 carbon atoms, and R represents a phenyl group optionally substituted by fluorine or chlorine or by an alkyl group of l-6 carbon atoms.

water and the resulting formulations applied at two dosage levels corresponding to 10 and 1 kilograms of active material per hectare respectively in a volume equivalent to 400 litres per hectare. In the soil drench substituted by alkyl phenyl,

tests one volume of the acetone solution was diluted to R I55 volumes with water and the resulting formulation dioxolan-Z-yl )carbonyl )-N -methylurea; N-( 4- benzyl-oxymethyl-Z-methyl-4-propyll ,3-dioxolan- Z-yl )carbonyl)-N '-metl1ylurea; N-((4- benzyloxymethyl-2,4-dimethyl-1,3-di0xolan-2- yl)carbonyl)-N'-butylurea; N-((4- benzyloxymethyl-2-methyl-4-ethyll ,3-dioxolan-2- yl )carbonyl )-N'-ethylurea or N-((4- benzyloxymethyl-Z-methyl-4-methy|- l ,3-dioxolan- 2-yl )carbonyl )-N'-cyclohexylurea. 

1. AN AMIDE DERIVATIVE OF THE FORMULA
 2. An amide derivative according to claim 1 wherein R3 represents a carbamoyl group N-substituted by alkyl or cycloalkyl of up to 6 carbon atoms, or by phenyl, tolyl or dichlorophenyl; and R4 represents a phenyl group optionally substituted by one or two chlorine atoms or by an alkyl group of 1-6 carbon atoms.
 3. A compound according to claim 1 wherein R1 is methyl, ethyl or propyl; R2 is methyl; R3 represents carbamoyl N-substituted by methyl, ethyl, propyl or butyl; and R4 represents phenyl.
 4. An amide derivative according to claim 1 which is selected from N-((4-benzyloxymethyl-2-methyl-4-ethyl-1,3-dioxolan-2-yl)carbonyl)-N'' -methylurea; N-((4-benzyl-oxymethyl-2-methyl-4-propyl-1,3-dioxolan-2-yl)carbonyl)-N'' -methylurea; N-((4-benzyloxymethyl-2,4-dimethyl-1,3-dioxolan-2-yl)carbonyl)-N''-butylurea; N-((4-benzyloxymethyl-2-methyl-4-ethyl-1,3-dioxolan-2-yl)carbonyl)-N''-ethylurea or N-((4-benzyloxymethyl-2-methyl-4-methyl-1,3-dioxolan-2-yl)carbonyl)-N'' -cyclohexylurea. 